Method for making oil gas and water gas



April 7, 53 R. T. COLLIER 2,634,197

METHOD FOR MAKING OIL GAS AND WATER GAS Filed Oct. 9, 1944 28b 26 OIL 6145 12 SEPARATo/Q x 27 34a- 30 F1. us 6A5 29 W4 75/? Gas GENERATOR v U \REACTOI? J -$TEAM FLU; 3.9 11 Gas HEflTEE IQV- 14 36 FUEL 4* fl/R d. 1

11555; L), v 10 mv $700K 1 .Z NVENTOE Ross/P7. Z COLL/5E a y Ham/5E i050; Foam? dq-Hnee/s Q N.) M

a conventional system of comparable size, as well as insuring more uniform products and reducing the frequency of shut-downs for cleaning or replacement of the refractory material.

A further object of the invention is to provide 7 such a process and apparatus in which a flow of hydrocarbon material to be subjected to pyrolysis carries the flow of the refractory material or heat transfer medium through the reaction zone in intimate relation to the hydrocarbon. As will be understood, increased intimacy of contact between the particles of the heat transfer medium and the fluid hydrocarbon to be thermally decomposed substantially increases the efliciency of the operation and reduces the period during which the hydrocarbon must be in the reaction chamber for the extent of thermal decomposition desired.

Another object of the invention is to provide an apparatus and process for the thermal decomposition of hydrocarbons in which solid carbonaceous decomposition products are carried out of the reaction chamber by a flow of the refractory material used to cause the thermal decomposition.

Still another object of the invention is to provide such a process and apparatus in which the flow of hydrocarbon material to be subjected to pyrolysis carries the heated refractory material or'heat transfer medium upwardly through the reaction zone and in which the refractory material returns to the heating zone from the reaction zone by gravity. This eliminates mechanical handling of the heat transfer medium, which is an important object of the invention. The importance of this feature of the invention will be recognized by those skilled in the art, as in the art of catalytic cracking of hydrocarbons it is sometimes the practice to provide elaborate and costly mechanical apparatus to transport a catalyst from one part of the apparatus to another. Although this feature of my invention might profitably be employed in such catalytic cracking processes, it will be apparent that it is of even greater value in a method of pyrolysis in which the temperatures employed (i. e., well above 1800 F.) are substantially higher than those employed in such catalytic cracking (i. e., below 1200 F.), because it is impractical, or even impossible considering the present state of the art, to build mechanical conveyors that will withstand the temperatures in excess of 1800 R, which I propose to use in my process.

It is also conventional practice in the art to form watergas, which is a term loosely given in the art to a mixture of hydrogen and carbon monoxide, by blowing steam through a bed of glowing coal or coke. It is a further object of my invention to utilize my present method and apparatus to form such a water gas as a byproduct of the process, when desired, which can be separately collected and stored or used. I prefer to accomplish this by blowing steam into intimate contact with the heated refractory material as it passes between the reaction zone and the heating zone, the steam reacting with carbonaceous material adhering to the refractory material, as a result of pyrolysis, to form such water gas. The formation of such water gas generally should be intermittent, while the formation of the oil gas is preferably continuous, to permit heating of the refractory material alternative to the formation of the water gas, and this is another object of the invention.

Other objects and advantages of my invention will become apparent from the following specification and the drawing, which is wholly diagrammatic and for illustrative purposes only.

Referring to the drawing, I show an apparatus including the following principal units: a tube furnace ID, a reactor H, a separator 12, a generator l3, and a heater I l.

The tube furnace ill is of conventional form, being provided with an inlet tubin 16 which is adapted to convey a liquid hydrocarbon, such as, for example, crude oil, into a heating coil I! disposed in the furnace and which is adapted to be heated by a conventional burner l8 impinging on the coil tubing. A flue i9 is provided on the furnace [B to dispose of combustion products of the burner l8.

The upper end of the heating coil IT is connected through a tubing 26 with th lower end of the reactor 1 i. The reactor l is a closed cylinder preferably disposed vertically,-which is in open communication at its lower end with the tubing 20, and at its upper end is in open communication with a preferably flared tubing 24 which connects the reactor and the separator l2. The tubing 2 3 preferably communicates with the separator 12 through a side wall 25 for convenience, but it will be apparent that the point of entry may be otherwise disposed without departing from the spirit'of the invention. Connected preferably to the top of the separator i2 is an oil gas tubing 26 adapted to convey gas from the separator to a point of storage or disposal (not shown) and having a gas valve 28 therein. Also connected to the upper end of the separator I2 is a vent tubing 28a having a vent valve 28b therein. The separator i2 is preferably provided with a conical bottom 21 adapted to guide granular material from the separator into a substantially vertical tubing 29 connected to the lower end of the conical bottom 21, the lower end of the tubing 29 being connected to the upper portion of the generator IS.

The generator i3 is in effect a closed tank, preferably having a water gas tubing 30 and a flue gas tubing 3| communicating with the upper end thereof and leading to suitable points for storage or disposal (not shown) and having valves 34 and Ma, respectively, therein. The generator I3 is also preferably provided with a conical bottom member 32 adapted to guide granular material from the generator into a substantially vertical tubing 33. Communicating with the bottom member 32 is a steam tubing 35 which leads to a suitable source of steam (not shown). Although the steam tubing 35 is diagrammatically shown, for simplicity, as a single tubing connected to the generator l3, it will be understood by those skilled in the art that in practice the steam tubing should be connected to the generator by a series of conventional tuyeres communicating with the interior of the generator. The lower end of the tubing 33 is connected to the upper portion of the heater Hi.

The heater I4 is also, in eifect, a closed tank, being preferably provided with a conical bottom element 36 adapted to guide a granular material from the heater into the upper end of a substantially vertical tubing 31, the lower end of which opens into the tubing 20 and is connected thereto through a gate valve 31a. Also connected to the bottom element 36 is an air tubing 38 which leads to a suitable source of air under pressure (not shown), and should in practice be provided with conventional tuyeres, as pointed out above with regard to the generator l3. Communicating with the top :01 1:4 is a flue seas tubins it! having 5a {gas valm 2:111. zthesem. Communicatin between the air tubing 38 the steam "tubing 3511s :a secondary :tuhing ill, z'the lower end :of whirl: ais in zopen .ccommumeation with the ,airztubing $3.8 dihe upper of "which .oommunicates with the steam tubing 35 through ;a two-way val-Me Ml. llzhc Waive 41! ism-ranged so that steam may l-ibe :adznittedrtothergenerator 1-3 through the tiihing13'5 :or so that iair may be admitted theneto through the itubings 3B and'39, aAlsoaconneoted to the bottom :element'dfi zadnel tubing :41 leading from a suitable source 40f iuel mot ishomm l,

such zas gas :or soil, and, rdesired, 3a :burner imay be employed in moniunetion mherewith in the heater i i to hurn $211201 gas, :as :is well 'known in I the .art. Entering :in'to theitub-ing Miadiacentits connectionmiithdzhe ztubingfll) fis .anziniectionz-tiibing 41a adaptedto iinject in jet aof fluid, such :as gets, under pressure from sa suitable source Knot shown) into liihE :tubhrg 18:1 Linbbhe direction of the tubing :29. 7

- Communicating With 1311311111817 ztiibing 1| s is a valved itu'bing 4.2,, adapted to admit a liquid the "inlet tubing :from a suitable source of supply (not shown? and for a purpose ,to :be described hereinafter. will :he understood :by lthose skilled "in ith'e east, the reactor .1 [,the separator m, =tlregenerator IS, the heater .i Azandithe ltUb-' in'gs connecting themfmap be lined with :carborundum, or other heat refractory material, to

confine and resist the temperatures utilized in the apparatus. i l

"5B0 prepare for operation of ethe'apparatus, ithe "heater I4 :is filled "with a sheet rtransfer :medium eornprised o'f a plurality of solididiscretezparticlesg a EGO-mesh "screen. Such particles are initially introduced into the heater 14 :b-y'temporarilyremom'ng the top itherefrom :orzotherwise :as may be desired, and fill the wertical tubing L-3s1 down to the ga'te valve 31a, which iis initially closed. *Insome-uses:oflthe apparatusritnnaysalso' be desirable to fill --the generator 1!:3 withrsuch 1a sudh ias, ilor example, isiliconrcarbide, ithe mtidles preferably being :of fSllGh rs'ize ithat they will pass through a fourqnesh lscreen but will mot :pass' heattransfermediumnso as to increaseithesupply I thereof in the system.

Before operation, the heat transfier smeclium the heaiter t 4 tmust' initially be heated -toxa desired f operating temperature, ZIo accomplish :this, a mixture of air an'diul, such-as gas or oil, rislzblotvn intoth'e heater Mthroug'hthe liuelftubing $4.1 :and

ignited in #Ithe heaitert liirin'g of the :contents :of

theheater M is continued untildzhe particles comprising' the heal; transfer medium therein brought to a desired elevated temperature, such.

as, for example, a temperature between N325.

erative furnace, and various means of iinitiazlly bringing such a furna'ce up to operating temperature are We'll known in 'the art, zany- 0f isuc'h fc'onveritional "means being-=contemplated byithezpresent invention. While the heater l l is losing brought up to operating temperature, .the :tube

furnace t'llFisalsoiired tmbringit up toiits operat-' system "from the inlet tube 48, passing throug'h the heating coil f! oi-the tube 'fiirnace ill :and

in the heater M.

smasher 6, i being preheated therein iby the :bumer 11-8 to la; temperature at which :part or all of rharging stock 'saporizes but :below the temperature :at

which any substantial whacking, ,or thermal x1ecomposition, of :the charging stink iw "511K311 as, ior example, :a temperature between 28011 I. and 11 .000 .1 1. 'llheheatingicoil 1:! thus defines 1a preheating :zone of the :apparatus. vaporization of :the charging vstockinatl ie daube furnace 1-0 substantially .incneases .the volume of the :charsing stock, which idows at relativelymigh velocity :but relatively low pressure atsuch -as, forcxample, :ten to "fifteen poundsiper square inch. :althoughhigher pressures may be utilized :if desired) .irom ithe tube :fn-rnacezthrough the tubing ,2 0, "upwardly through the reactor I], through the tubin iu,

"and into the separator L2 The initial -;fl0.w ,iUf

charging stock vapors may The :vented from, the separator 2512 by olosingithe gaswalve 12B :and 10pming the'vent valve 28b, "to permit :the initial :flow of :charging istock vapors .to 'ilow'irom'the separator through :the 21 761113 tubing 12811 to :a suitable point of disposal :inottshovm). This -is normally continued .untilxtlre temperature of the :tubin s 2-3 and 21, :the reactor l I, and the separator M has been substantially raised bythe .fiowsof :heated vaporized .chargingstorik'thfiethrough.

As soonnas'the desired volume of flow of vaporized preheated 1charg'ing stock ilowingithrough the tubing 21), thejgate rahlefila isopenBdLtOzpermil; the head; transfer medium tolfiow by *g-IEMHKY downwardly irom the heater 1:.4 .iinto "the'ztubing 21 51, a suitable :fiuicl, such :as a gas, preferably theing injected into the :tubing r3! from the injection tubing 41a to assist ithe movement of the heat (transfer medium into the tubing .20.. As heretofore indicated, there :is a ffluid pressure above atmospheric pressure in ;the;.tubing&i1,

which is normally higher :ithan =.the tfluid pressure Consequently, :to facilitate movement of :the heat transfer medium through,

the tunings :froin :the heater 414 it!) :the :tub-,

ing .29, the injection atubin-g Aid is employed to create :a:fluid pressure Ediiferential between the ends .nf the tubing "3?! carpableaof assisting :such movement :of .fheatitransfer medium 'therethrough and to eliminate backtpressure ;,to:the heater iii. A jet :action :of :the teas issuing ifrom the injection tubing 4111 into .the tubing ,3] is ,alsordesi-rable to .sassist :such :movement of :the heat transfer medium :and iurther serves, :When desired, :gas "a means whereby diluent ;-:gas may be injected into the 350w :of icharging :stock the tubing 32a,- to assist 101 replace the operation of the tubing 42. the lhozt :heat transfer :medium flows into the :tubing r29, :it is :carried -.ther.ethrough by the :flow or charging, :stock vapors therein :into :the

reactor '31:! and :upwardly :therethrough'ithrough thefiow passage 32:3,:dischargi11g through 1the;11ub-' ing :24 :intoflzhe separator 12. .As-will be widerstood, the :supply of fuel to the heater lAis-con tinueduntil callof fthe-heat transfer medium initially :in :the :system heated :to operating temperature.

"Due to the Qliigh :temperature acquired by the heat itransfer zmediumiin "the heater -14, as soon as the heat. transfer medium enters the stream sci charging stock Manors passing: through the tub ing it, pyrolysis of thercharging stool; zvapors commences-end :is continued :as the vapors-rand heat transfer medium pass .;in intimate contact through the reactor Ll, :most of 'such pyrolysisoccurring :in the reactor. 'Thll$ the interior of the reactor all may be :termed areaction ,zone, although :it will he understood that pyrolysis commences to occur upon'contact of the heat transfer medium with the charging stock vapors in the tubing 20. As will also be understood, the intimate contact of the heat transfer medium with the charging stock vapors raises the temperature of the latter to between 1800 F. and 2200 F. in the reaction zone in the reactor 1 I, at which temperature the charging stock is thermally decomposed to produce oil gas or other light gaseous products and solid carbon or carbonaceous material. The bulk of the carbon or solid carbonaceous material which results from the thermal decomposition of the charging stock in the reactor ll normally adheres to the particles of the heat transfer medium and is carried thereby from the reactor I I.

The gaseous products of pyrolysis in the re actor I I then carry the stream of particles of the Y heat transfer medium, having carbon or carbonaceous material adhering thereto, from the top of the reactor, through the flared tubing 2 3, and into the separator I2, which may be defined as a separating zone of the apparatus, designed to separate such gaseous, products from the heat transfer medium. Due to the flare of the tub ing 24 and the increased cross-sectional area of the separator I2, the velocity and pressure of the gaseous products flowing into the separator from the reactor II are materially reduced, and the particles of heat transfer medium settle to the bottom of the separator, and the gaseous products tend to collect in the top thereof, thus separating the gaseous products from the heat transfer medium. As soon as gaseous products of pyrolysis start to collect in the top of the separator I2, the vent valve 281), may be closed, and,

the gas valve 23 may be opened to permit such gaseous products to discharge from the separator through the oil gas tubing 26. Although the separator l2, as illustrated, is of a simple gravity type, it is to be understood that I do not desire to be limited thereto, but intend to include any desired type of separator adapted to separatethe gaseous products of pyrolsis from the heat transfer medium, such as, for example, any of the mechanical or electrical separators well known in the art adapted for that purpose.

Particles of the .heat transfer medium collecting in the bottom of the separator i2 flow downwardly therefrom by gravity through the vertical tubing 29 into the generator i3, which defines a generating zone of the apparatus. The valves 3 and 34a are alternatively opened and closed forpredetermined periods. When the valve ,34 is opened and the valve 34a is closed, the valve 40 is adjusted to admit steam fromthe steam tubing -35 into the lower end of the generator 13., Steam,

admitted into the bottom of the generator 13 passes upwardly in intimate contact with thehot particles of heat. exchange material therein and reacts, as is well known in the art, with the carbon or carbonaceous material adhering to the particles to form water gas,- which is discharged from the generator through the water gas tubing 30 Such generation of water gas in the generator i3 is continued for a brief cycle, such as, for example, 120 seconds, and the valve 34 is then closed, the valve 34a. is opened, and the valve 40 is adjusted so as to permit air under pressure to pass from the tubing 39 through the tubing 35 into the bottom of the generator and blowthrough the particles of heat transfer me-' dium therein. Such passage of air in intimate contact with the particles of heat transfer medium burns or oxidizes a substantial portion of the remaining carbon from the particles, produc-' ing heat and flue gas. Theheatv produced by such oxidation of the carbon raises the temperature of the particles substantially, the gaseous products of such combustion being discharged as flue gases from the generator 13 through the flue gas tubing 3|. As will be understood, the passage of air and steam upwardly in the generator l3 agitates the particles of heat transfer medium therein and prevents packing or caking thereof. The operation of the generator 13 is thus preferably such that water gas is intermit-,

tently generated therein.

The particles of heat transfer medium, largely decarbonized and in partreheated, then pass by gravity'downwardly through the tubing 83 into'the heater I4, which defines a heating zone of the apparatus, adapted toreheat the particles to the desired elevated temperature. After the supply of fuel gas to the heater l4 through the fuel inlet tubing 4! is discontinued following the initial heating of the particles, air under pressure is thereafter continuously blown through the heater from the air tubing 38, which oxidizes or burns the remaining carbon adhering to the particles, to again raise the temperature of the particles to the initial operating temperature and to" form flue gas which is discharged therefrom through the fluegas tubing 2|, and which keeps the particles agitated to prevent packing or caking thereof.

The average length of time that each particle of the heat transfer medium remains in the heater M depends in large measure on the amount of carbonaceous material formed in the reactor II and the temperature to which it is desired to reheat the particles. As is well known in the art, the amount of such carbonaceous material formed depends largely on the nature of the charging stock, e. g., using a heavy charging stock, such as still bottoms, large amounts of carbon are formed, whereas using a light charg ing stock, such as gasoline or gas oil, only relatively small amounts of carbon are formed. In practice, the average heating portion of the particle' cycle is normally less than four minutes. The reheated particles of heat transfer medium may then again pass by gravity downwardly through the vertical tubing 31 into the tubing 20, to start a new cycle through the apparatus. The extent of heating in the heater l4, and consequently the-temperature attained therein, may be controlled by regulating the amount of car bon remaining on the particles passing into the heater from-the generator 13 by regulating the amount of oxidation and heating in the generator.

It will thus be understood that my process is continuous to produce products of pyrolysis of the charging stock, such as oil gas, which 7 is continuously withdrawn from the apparatus for further processing, storage, or disposal. As will also be understood, the fact that I convey the heat transfer medium continuously through the apparatus, alternately heating it and using it to provide the high temperature required for pyrolysis, provides the continuous operation of the method, which is a primary object of the invention. The result of the practice of my method of continuously heating and then conveying a flow of heat transfer material through a reaction zone, such as provided by the reactor H, is to maintain the reaction zone at an optimum desired temperature most efficient for the thermal decomposition of the hydrocarbons desired.

smears? The. manufacture. of waterzgas, as described above; may, of: course, be. omitted; from the; promess: if: desired. This: is. donebymerely setting the valves. 34 to its closed position, the. valve: 34a being; opened, and. the; valve 40 being. adjustedso as to. convey air. from. the air tubing 38; through the tubings- 39 and 35- into: the generator I53 to partiallyoxidize thecarbon on the heat transfer medium therein to, reheat, partially the particles, thebalance of. the reheating, being, accomplished irrthe. heater: [4 as described above; If, it is; not desired. to incorporaterthe water gas; forming. step into. the apparatus; the generator: 13; may also be omitted entirely from the apparatus connecting the; vertical tubings; '2 9= and 3.3 in direct, communication.

If it isidesired to manufacture.v water gas; continuously with my apparatus, this may be: ac complished. by maintaining the; valve;- 34 con.- tinuously open,.the valve 34a continuously closed, and the valve ib; so: as v to permit. a continuous flow of steam from; the: steamy tubing 35 through. the

, generatorl3-. In this variation of the process,

While I, have; mentioned. crude: petroleum. oil

as the: charging stock used in the process, it will be apparent to: those. skilled: in. the. art that a large variety of; petroleum. substances. may be utilized as the charging stocks Consequently, whenever I. refer to. crude. oil herein, I desire to include. within. the meaning of the; term not, only crude oil, but. other suitable petroleum; materials, such as, for example, gas. oil, topped or; reduced crude oil, cracking stillbottoms, asphaltic; ma.- terials, and the like, which; are sufficiently liquid to be: conveniently passed through; tubing; and vaporized: and, thermally decomposed. at. the high temperatures contemplated, to? formv oil gas; or other light products of. thermal decomposition, such as, for example, acetylene, ethylene, butylene, propylene, ethane, methane, and the like.

In the event that heavy crude oil, liquid asphalt, or still bottoms; are: used. for the; charging stock, it is frequently desirable to dilute thev same This" may be accomplished; by introducing a. flow of liquid diluent, such as, for example, gas oil, from a suitable source of supply (not shown). through the tubing 42 into the chargin stock flowing to the apparatus: If desired, however, a. gaseous diluent may be introduced into the tubing 20' through the tubing Ala, as described above; so as to mix with the vaporized charging stock passing through the tubing; 20 from the tube furnace liiefor'ethe vaporized charging stock contacted; by; particles of the heat, exchange mediumv issuing, from the vertical tubing 31...

The heat transfer medium. used in my proccs asiwillbe evident from. theforegoing descripin natura. The; particles: must; also be large enough. to; separate; or be; separated readi y from the. reaction. product; gases. in the separator t2 and. to pass readily downwardly through; the separator;,. the: enerator l3, and. the, heater M cnuntercurrent tdth nrpwardefiow of air-or steam in the; generators or heater; and large: enough so that; they willinotnackz in: the a paratus and stop the: W, therethroughr Consequently;, it: is preferabl-e; toe useparticles; of. a size such thatthe ma,- iorizty' thereof, will not. pass through a: LOO-mesh screen although larger particles; may be; used: if desired. Onthe other hand, it. is necessarytouse. particles small enough: that: they may flow readily through the apparatus and be: carried Without, di-ihculty' by the-vaporizedcharging stock and the reaction product: gases;' and; to.- accomplishthese purposes it. ispreferable toj use: partis c-lesiallof which aresmallenough to pass: through afour-mesh screen.

The heat transfer medium, as pointed out above, is preferably silicon. carbide. Thisi's due to thefact that silicon carbide hashigh heat re,- sistivity, thermal conductivity, melting point, modulus of. rupture and a relatively high porosity, all of. which qualities are of importance in the-practice of. my process. It is-to be understood, however, that any other solidmaterial having. such. suitable. physical. characteristics, may be used Without departing fromthe spirit of my invention, so long as it does not. substantially enter into the. thermal decomposition reactions occurring inthe reactor ll...

Although my apparatus is primarily intended toioperate; as a low-pressure system, at relatively low pressuresv such,,f.or example, as ten. to fifteen pounds per square inch, I do. not intend to be limited. thereto. The pressures, used need only be high. enough to insure a gas velocity through the apparatus sufficient, totransport the heat transfer medium. therein as described. above, although, obviously, considerably higher pressures may be. usedif. desired.

Whilev my invention isv adapted to the. pyrolysis of, a Wide. range of. hydrocarbons usedas a charging, stock, as. described, it, is of, particular value, in connection with the use of. so-calledheavy hydrocarbons. which produce relatively large amounts of carbonaceous material. upon pyrolysis. For example, whereas. in. the catalytic Cr art it has beenimpractical or impossible heretoforetoutilize suchheavy hydrocarbons due to, the, difiiculties of removal and, disposal ofQthe relatively great. amounts. of carbonaceous ma.- terial which. would, be formed during, cracking, my invention makes the use of such heavy hydrocarbons as, charging stock. not only possible, but, advantageous, as it provides a cheap charging, stock. and permits the. manufacture. of water gas a a. valuable. by-product. of the. process.

While. I have shownand described apreferred embodiment of the. invention, and certain variations. thereof, I. do not. desire: to be, limited by such. specific description, but. desire to be. afiforded. the. fullscope oflthe. following claims.

Iiclaiin. as my invention p 1 A method of pyrolysis of hydrocarbbnsiinr cluding the steps of: forming a flow of fluid hydrocarbon material conveying a plurality of discrete non-carbon particles of a heat transfer medium through a reaction zone in which gas is formed and the rate of flow inhibits settling, and into a separating zone in which particles separate from said gas; moving particles from said separating zone to a generating zone and to a heating zone; heating a plurality of said non-carbon particles in said heatingzone to a temperature in excess of 1800 F. adapted to cause pyrolysis of said hydrocarbon; introducing a stream of said heated particles from said heating zone into said flow so as to be carried thereby through said reaction zone to said separating zone, at least a portion of said hydrocarbon being converted by pyrolysis in said reaction zone by contact with said heated particles to form a resultant gas and a solid carbon product, some of said carbon adhering to said particles; separating said gas from said particles in said separating zone; passing steam in intimate relation with said particles in said generating zone to form water gas; separating said water gas from said particles; conveying said particles from said generating zone to said heating zone; and reheating said particles in said heating zone to a temperature in excess of 1800 F. and removing all free carbon from said particles.

2. A method of pyrolysis of hydrocarbons, including the steps of forming a flow of fluid hydrocarbon material adapted to convey a plurality of discrete particles of a heat transfer medium through a reaction zone to a separating zone; passing particles from said separating zone to a generating zone, and to a heating zone; heating a plurality of said particles in said heating zone to a temperature in excess of 1800" F. adapted to cause pyrolysis of said hydrocarbon; introducing a stream of said heated particles from said heating zone into said flow so as to be carried thereby through said reaction zone and into said separating zone, at least a portion of said hydrocarbon being converted by pyrolysis in said reaction zone by contact with said heated particles to form a resultant gas and a solid carbon product, some of said carbon adhering to said particles; separating said gas from said particles in said separating zone; passing steam in intimate relation with said particles in said generating zone to form water gas with adhering carbon; separating said water gas from said particles in said generating zone; through said particles in said generating zone to oxidize carbon thereon and thus heat said particles; conveying said particles from said generating zone to said heating zone; and reheating said particles in said heating zone to a temperature in excess of 1800 F.

3. A method of pyrolysis of hydrocarbons, including the steps of: forming a flow of fluid hydrocarbon material adapted to convey a plurality of discrete particles of a heat transfer medium through a reaction zone in which gas is formed and the rate of flow inhibits settling, and thence into a separating zone wherein particles separate from said gas; passing separated particles from said separating zone to a generating zone, and to a heating zone; heating a plurality of said particles in said heating zone to a temperature in excess of 1800 F. adapted to cause pyrolysis of said hydrocarbon; introducing a stream of said heated particles from said heating zone into said flow so as to be carried thereby through said reaction zone to said separating zone, at least thereafter passing air a portion of said hydrocarbon being converted by pyrolysis in said reaction zone by contact with said heated particles to form a resultant gas and a solid carbon product, some of said carbon adhering to said particles; separating said gas from said particles in said separating zone; alternatively passing air and steam through said particles in said generating zone, said air causing oxidation of a portion of said carbon to heat said particles and said steam forming water gas; conveying said particles from said generating zone to said heating zone; and reheating said particles in said heating zone to a temperature in excess of 1800 F.

4. A method of pyrolysis of hydrocarbons, including the steps of: forming a, flow of fluid hydrocarbon material adapted to convey a plurality of discrete particles of a heat transfer medium in turn upwardly through a reaction zone, in which the rate of flow is maintained to inhibit settling of said particles, and into a separating zone from which said particles can pass by gravity through a generating zone and into a heating zone; heatin a plurality of said particles in said heating zone to a temperature in excess of 1800 F. adapted to cause pyrolysis of said hydrocarbon; introducing a stream of said heated particles from said heating zone into said flow so as to be carried thereby upwardly through said reaction zone and into said separating zone, at least a portion of said hydrocarbon being converted by pyrolysis in said reaction zone by contact with said heated particles to form a resultant gas and a solid carbon product, some of said carbon adhering to said particles; separating said gas from said particles in said separating zone; permitting said particles to pass by gravity from said separating zone into said generating zone; treating said particles in said generating zone with steam to form water gas from a portion of said carbon adhering to said particles; permitting said particles to pass by gravity from said generating zone to said heating zone; and reheating said particles in said heating zone to a temperature in excess of 1800 F.

ROBERT T. COLLIER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,875,923 Harrison Sept. 6, 1932 1,992,909 Davis Feb. 26, 1935 2,325,516 Holt et al July 27, 1943 I 2,331,433 Simpson Oct. 12, 1943 2,340,814 Lidov Feb. 1, 1944 2,405,395 Bahlke et al Aug. 6, 1946 2,443,714 Arveson June 22, 1948 FOREIGN PATENTS Number Country Date 533,037 Germany Sept. 8, 1931 561,899 Germany Oct. 19, 1932 23,045 Great Britain Aug. 24, 1911 of 1910 

1. A METHOD OF PYROLYSIS OF HYDROCARBONS, INCLUDING THE STEPS OF: FORMING A FLOW OF FLUID HYDROCARBON MATERIAL CONVEYING A PLURALITY OF DISCRETE NON-CARBON PARTICLES OF A HEAT TRANSFER MEDIUM THROUGH A REACTION ZONE IN WHICH GAS IS FORMED AND THE RATE OF FLOW INHIBITS SETTLING, AND INTO A SEPARATING ZONE IN WHICH PARTICLES SEPARATE FROM SAID GAS; MOVING PARTICLES FROM SAID SEPARATING ZONE TO A GENERATING ZONE AND TO A HEATING ZONE; HEATING A PLURALITY OF SAID NON-CARBON PARTICLES IN SAID HEATING ZONE TO A TEMPERATURE IN EXCESS OF 1800* F. ADAPTED TO CAUSE PYROLYSIS OF SAID HYDROCARBON; INTRODUCING A STREAM OF SAID HEATED PARTICLES FROM SAID HEATING ZONE INTO SAID FLOW SO AS TO BE CARRIED THEREBY THROUGH SAID REACTION ZONE TO SAID SEPARATING ZONE, AT LEAST A PORTION OF SAID HYDROCARBON BEING CONVERTED BY PYROLYSIS IN SAID REACTION ZONE BY CONTACT WITH SAID HEATED PARTICLES TO FORM A RESULTANT GAS AND A SOLID CARBON PRODUCT, SOME OF SAID CARBON ADHERING TO SAID PARTICLES; SEPARATING SAID GAS FROM SAID PARTICLES IN SAID SEPARATING ZONE; PASSING STEAM IN INTIMATE RELATION WITH SAID PARTICLES IN SAID GENERATING ZONE TO FORM WATER GAS; SEPARATING SAID WATER GAS FROM SAID PARTICLES; CONVEYING SAID PARTICLES FROM SAID GENERATING ZONE TO SAID HEATING ZONE; AND REHEATING SAID PARTICLES IN SAID HEATING ZONE TO A TEMPERATURE IN EXCESS OF 1800* F. AND REMOVING ALL FREE CARBON FROM SAID PARTICLES. 